Golf club made of a bulk-solidifying amorphous metal

ABSTRACT

A golf club is made of a club shaft and a club head. Either the club shaft or the club head is made at least in part of a bulk-solidifying amorphous metal. A preferred bulk-solidifying amorphous metal has a composition, in atomic percent, of from about 45 to about 67 percent total of zirconium plus titanium, from about 10 to about 35 percent beryllium, and from about 10 to about 38 percent total of copper plus nickel, plus incidental impurities, the total of the percentages being 100 atomic percent. The weights of the various club heads of a set, which have different volumes, may be established by varying the compositions and thence the densities of the bulk-solidifying amorphous alloys.

CROSS-REFERENCE TO RELATED CASES

This application is a continuation of pending application Ser. No.08/963,131, filed Oct. 28,1997, for which priority is claimed, which inturn is a continuation-in-part of abandoned application Ser. No.08/677,488, filed Jul. 9, 1996, for which priority is claimed, which inturn is a continuation-in-part of abandoned application Ser. No.08/566,885, filed Dec. 4, 1995, for which priority is claimed.

FIELD OF THE INVENTION

This invention relates to golf clubs, and, more particularly, to thematerial of construction of the golf club shaft and the golf club head.

BACKGROUND OF INVENTION

In the sport of golf, the golfer strikes a golf ball with a golf club.The golf club includes an elongated club shaft, which is attached at oneend to an enlarged club head and is wrapped at the other end with agripping material to form a handle. The clubs are divided into severalgroups, depending upon the function of the club. These groups includethe drivers, the irons (including wedges for the present purposes), andthe putters.

Because golf has become a highly popular spectator and participantsport, a great deal of development effort has been devoted to golfclubs. Both the design of the clubs and the materials of constructionhave been improved in recent years. The present invention dealsprimarily with the materials of construction of golf clubs, and thefollowing discussion will emphasize that subject area.

Until recent years, both the club shaft and the club head have been madeprimarily of metals such as steel and/or aluminum alloys.Composite-material shafts made of graphite-fiber-reinforced polymericmaterials have been introduced, to reduce the weight and increase thematerial stiffness of the shaft. Heads made of specialty materials suchas titanium alloys have been developed, to achieve reduced club headmass and density with high material stiffness so that the club headspeed may be increased. The use of such materials also permits themanufacture of a larger-sized club head with the same mass or withredistributed weight and better performance. This brief discussion ofnew materials used in golf club shafts and heads is by no meansexhaustive, and many other materials have been tried in order to achieveparticular club behavior based upon various theories of clubperformance.

There remains a need, however, for further improvements in golf clubs inorder to attain high material stiffness, high stiffness-to-weight ratio,and high strength-to-weight ratio. These properties, in turn, lead tohigher club head speed and a higher degree of energy transfer from theclub to the ball upon impact, thereby permitting any player to performto the best of his or her ability without being limited by the nature ofthe golf clubs. The present invention fulfills this need, and furtherprovides related advantages.

SUMMARY OF THE INVENTION

The present invention provides a golf club with an improved material ofconstruction. The golf club exploits the unusual elastic properties ofthe material to provide a high degree of energy transfer from the clubto the ball upon impact. The club is also corrosion resistant, wearresistant, and has a low coefficient of club head face friction. Theclub shaft and head are readily fabricated. For some clubs, the materialof construction permits the configuration of the golf club to bemodified so as to improve its performance.

In accordance with the invention, a golf club comprises a club shaft anda club head. Either or both of the club shaft and the club head are madeat least in part of a bulk-solidifying amorphous metal. If the clubshaft is made at least in part of a bulk-solidifying amorphous metal,the entire shaft is desirably made of the bulk-solidifying amorphousmaterial. If the club head is made at least in part of thebulk-solidifying amorphous metal, at least the club head face is made ofthe bulk-solidifying amorphous material. The club head face may be madethinner and lighter when it is made of the bulk solidifying amorphousmetal than when it is made of conventional metals, allowing a desirableredistribution of the weight of the club head toward the periphery ofthe club head.

A preferred composition for the bulk-solidifying amorphous metal is, inatom percent, from about 45 to about 67 percent total of zirconium plustitanium, from about 10 to about 35 percent beryllium, and from about 10to about 38 percent total of copper plus nickel, plus incidentalimpurities, the total of the percentages being 100 atomic percent. Otherbulk-solidifying amorphous metals may also be used.

Manufacture of a portion of the golf club from a bulk-solidifyingamorphous metal yields surprising and unexpected improvements in clubperformance. If the club shaft is made of the bulk-solidifying amorphousmetal, it is stiff and strong. If the club head is made of thebulk-solidifying amorphous metal, it is stiff, strong, and hard, therebyresisting damage resulting from impact of the club head with the golfball. In both components, the amorphous metal sustains very high levelsof elastic deformation with essentially no plastic deformation. It hasbeen demonstrated that elastic tensile strains of up to about 2 percentare achieved with essentially no anelastic or plastic response of thematerial. Accordingly, the large elastic strains sustained during impactof the club head with the ball are accompanied by essentially noanelastic or plastic response. Consequently, virtually no energy isabsorbed during the deformation of the club head during impact with thegolf ball. A higher fraction of the energy of the golfer's swing istherefore transferred into the golf ball upon impact than in the case ofthe use of a material which exhibits a significant degree of absorptionof energy by anelastic or plastic deformation.

The approach of the present invention also permits the weights of thedifferent club heads in a club set to be varied independently of thevolume of the club head or in conjunction with the volume of the clubhead in an arbitrary manner. The shapes and volumes of different clubheads in a set vary. By custom and tradition, club weights increase froma 2-iron to a sand wedge. In the conventional approach, optimal designdeals with the shape (i.e., volume) of the club head. The weights of theindividual clubs cannot be varied outside of limits established eitherby professional standards or established user preferences. Whenconventional materials are used to make the club heads, the weights ofthe club heads vary directly proportionally to the volume of the clubhead.

According to the present invention, a set of golf clubs comprises afirst club having a first club head with a first volume and made of afirst bulk-solidifying amorphous alloy having a first composition and afirst density. The set further comprises a second club having a secondclub head with a second volume and made of a second bulk-solidifyingamorphous alloy having a second composition different from the firstcomposition and a second density different from the first density. Thefirst and second bulk-solidifying amorphous alloys are preferablyselected from the same alloy family, i.e., alloys whose compositions arewithin the same continuous range.

The compositions and densities within a bulk-solidifying amorphous alloysystem may be varied in small increments but over a wide range,permitting the weights of the club heads to be arbitrarily determined bycomposition selection within a wide range. An example is useful inillustrating this point. If it were desired that the club heads of twodifferent clubs should have the same weight, a first product of thefirst volume times the first density, the weight of the first club head,is made about the same as a second product of the second volume timesthe second density, the weight of the second club head. That is, forthis constant-weight situation the compositions of the alloys used tomake the club heads are selected so as to vary their densities inverselywith the volume of the club heads for which they are to be used. Knownbulk-solidifying amorphous alloy families permit such density variationwithin the range of feasible club head design variations. The sameprinciples are applied for the other clubs in the set. The golfer thushas a club set where the heads are of substantially constant weight,while also enjoying the other advantages of the bulk-solidifyingamorphous alloys.

The constant-weight example is just one case of the ability provided bythe present invention to arbitrarily vary the club-head weightsindependently of the club-head volume. The weights of the club heads ofthe set may instead be made to vary in some other fashion, independentlyof the club volume. This capability permits the club designer widelatitude in selecting club-head shapes and weights. The wide range ofweights and tailoring of the weights are achieved with a homogeneousalloy material, and without the use of cumbersome weights, plugs, orother inserts that alter the impact and mass-distribution properties ofthe club head.

Other features and advantages of the present invention will be apparentfrom the following more detailed description of the preferredembodiment, taken in conjunction with the accompanying drawings, whichillustrate, by way of example, the principles of the invention. Thescope of the invention is not, however, limited to this preferredembodiment.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a golf club;

FIG. 2 is an enlarged sectional view of the club shaft, taken alonglines 2-2 of FIG. 1;

FIGS. 3A-3C are three enlarged sectional views of three embodiments ofthe club head, taken along lines 3-3 of FIG. 1, wherein FIG. 3A depictsa putter club head, FIG. 3B depicts an iron club head, and FIG. 3Cdepicts a driver club head;

FIG. 4 are measured stress-strain curves for a titanium alloy and for abulk-solidifying amorphous alloy;

FIG. 5 is a measured graph of stress versus strain for a titanium alloyand for the preferred bulk-solidifying amorphous alloy (Vitreloy™-1)during cyclic straining of the materials;

FIG. 6A is a side sectional view of a first iron club head having afirst volume;

FIG. 6B is a side sectional view of a second iron club head having asecond volume; and

FIG. 7 is a block flow diagram of an approach for preparing a cast golfclub component.

DETAILED DESCRIPTION OF THE INVENTION

FIG. 1 depicts a golf club 20. The golf club 20 includes a club shaft 22and a club head 24 attached to a lower end of the club shaft 22. Ahandle 26 is formed at an upper end of the club shaft 22 by wrapping agripping material around the club shaft 22. FIGS. 1-3, showingembodiments of the club, club shaft, and club head, are somewhatschematic in form and are intended to generally portray these elements.There are many variations of the basic design configuration of the golfclub, and the present invention dealing with materials of constructionis applicable to all of these variations.

The club shaft 22 is elongated and generally rodlike in form. The clubshaft may be solid in cross section, or it may be hollow as shown inFIG. 2. The club shaft is preferably hollow in cross section in thepresent invention.

The club head 24 has many design variations, but they may be generallyclassified into three groups as shown in FIGS. 3. A putter club head 28(FIG. 3A) has a club head face 30 with bolsters 32 at the ends. The clubhead face 30 is usually roughly vertical to the ground when the golfclub is held by the user. An iron club head 34 (as used herein, ironsinclude wedges), shown in FIG. 3B, has a similar construction, with anumber of different angles of the club head face 30 to the groundavailable to aid the golfer to determine the loft of the shot. (The word“iron” is here a term of art for the type of club, and does not suggestthat the club head is made of the metal iron.) A driver club head 36 mayhave the basic form of the putter head, but more preferably has a moremassive, rounded body shape such as shown in FIG. 3C. As with the ironclub head, the angle of the club head face 30 to the ground of thedriver club head varies with different types of drivers. The club headface 30 may be integral with the body of the club head. The club headface 30 may include a separate plate 30′ that is fabricated separatelyand joined to the body of the club head, as shown in dashed lines inFIG. 3C.

Either the club shaft 22 or the club head 24 is made at least in part ofa bulk-solidifying amorphous alloy, preferably by casting the alloy toshape in a properly configured mold. Bulk-solidifying amorphous alloysare a recently developed class of amorphous alloys that retain theiramorphous structures when cooled from high temperatures at criticalcooling rates of about 500° C. or less, depending upon the alloycomposition. Bulk-solidifying amorphous alloys have been described, forexample, in U.S. Pat. Nos. 5,288,344, 5,368,659, and 5,032,196, whosedisclosures are incorporated by reference.

The golf club component made of the bulk-solidifying amorphous alloy ispreferably made by “permanent mold casting”, which, as used herein,includes die casting or any other casting technique having a permanentmold into which metal is introduced, as by pouring, injecting, vacuumdrawing, or the like. Referring to FIG. 7, a bulk-solidifying amorphousalloy, to be described in greater detail subsequently, is provided,numeral 40. A permanent mold having a mold cavity defining the shape ofthe golf club component, such as the golf club head, is provided,numeral 42. The bulk-solidifying amorphous alloy is heated to atemperature such that it may be introduced into the permanent mold,numeral 44. The bulk-solidifying amorphous alloy is cooled to relativelylow temperature, such as room temperature, at a rate sufficiently highthat the amorphous structure is retained in the final cast product,numeral 46.

This approach is to be contrasted with the processing used withconventional materials. Golf club heads made of conventional highstrength materials such as titanium and steel are investment cast by thelost wax process or forged to shape. Both techniques require finishingoperations such as machining and grinding. The investment castingprocess provides moderately low-cost products that are nottechnologically the equal of forged products, whereas forging provideshigher quality products at a substantially higher cost. The quality offorged products is due to the higher strength of forged metals, moreuniform and porosity-free structure, and better control of dimensionssuch as wall thicknesses than possible with investment casting.Investment cast products such as golf-club heads have lower strengthsdue to porosity, and they exhibit shrinkage in the casting operations. Adifferent mold is created from a wax pattern for each golf-club headthat is to be investment cast. Consequently, the dimensions of the golfclub head, such as its wall thickness, cannot be consistently reproduceddue to movement of the wax pattern and other factors. The resultingarticle may therefore vary significantly from the design. The variationsare such that some golf-club heads produced within the relatively widetolerances of the investment casting process may not be within therelatively narrow tolerances of the club design, and accordingly must bescrapped. The tolerances of forging operations are narrower, but forgingis considerably more costly than investment casting and typicallyrequires some machining of the product.

The golf-club components made by permanent-mold casting ofbulk-solidifying amorphous alloys overcome the shortcomings of the priorapproaches by achieving good tolerances with much lower cost thanpossible with either investment cast or forged golf club heads. Thegolf-club component closely matches the design. The bulk-solidifyingcomponents made by permanent-mold casting have low or negligibleshrinkage and porosity, leading to good strength and also to lowvariation in shape. They also exhibit excellent surface finish andreplication of the mold interior. There are no spurious features due tothe wax patterns sometimes found in investment cast articles or due tothe forging defects sometimes found in forged articles. Only a singlepermanent mold is used, or a group of permanent molds are used which arecarefully matched to each other because they are repeatedly used. Ineach case, the permanent mold or molds are carefully matched to the clubdesign. The permanent mold casting of crystalline alloys such astitanium alloys and steels, used in conventional golf club heads, is noteconomically practical because of the higher mold wear experienced withthese alloys, which have higher casting temperatures than knownbulk-solidifying amorphous alloys. The solidification shrinkage andconsequent warping of these conventional crystalline alloys also doesnot permit the net-shape casting possible with the bulk-solidifyingamorphous alloys.

Bulk-solidifying amorphous metal alloys may be cooled from the melt atrelatively low cooling rates, on the order of 500° C. per second orless, yet retain an amorphous structure. Such metals do not experience aliquid/solid crystallization transformation upon cooling, as withconventional metals. Instead, the highly fluid, non-crystalline form ofthe metal found at high temperatures becomes more viscous as thetemperature is reduced, eventually taking on the outward physicalappearance and characteristics of a conventional solid. Even thoughthere is no liquid/solid crystallization transformation for such ametal, an effective “freezing temperature”, T_(g) (often referred to asthe glass transition temperature), may be defined as the temperaturebelow which the viscosity of the cooled liquid rises above 10¹³ poise.At temperatures below T_(g), the material is for all practical purposesa solid. An effective “fluid temperature”, T_(f), may be defined as thetemperature above which the viscosity falls below 10² poise. Attemperatures above T_(g), the material is for all practical purposes aliquid. At temperatures between T_(f) and T_(g), the viscosity of thebulk-solidifying amorphous metal changes slowly and smoothly withtemperature. For the zirconium-titanium-nickel-copper-beryllium alloy ofthe preferred embodiment, T_(g) is about 350-400° C. and T_(f) is about700-800° C.

This ability to retain an amorphous structure even with a relativelyslow cooling rate is to be contrasted with the behavior of other typesof amorphous metals that require cooling rates of at least about10⁴-10⁶° C. per second from the melt to retain the amorphous structureupon cooling. Such metals may only be fabricated in amorphous form asthin ribbons or particles. Such a metal has limited usefulness becauseit cannot be prepared in the thicker sections required for typicalarticles of the type prepared by more conventional casting techniques,and it certainly cannot be used to prepare three-dimensional articlessuch as golf club shafts and heads.

A preferred type of bulk-solidifying amorphous alloy has a compositionof about that of a deep eutectic composition. Such a deep eutecticcomposition has a relatively low melting point and a steep liquidus. Thecomposition of the bulk-solidifying amorphous alloy should thereforepreferably be selected such that the liquidus temperature of theamorphous alloy is no more than about 50-75° C. higher than the eutectictemperature, so as not to lose the advantages of the low eutecticmelting point.

A most preferred type of bulk-solidifying amorphous alloy family has acomposition near a eutectic composition, such as a deep eutecticcomposition with a eutectic temperature on the order of 660° C. Thismaterial has a composition, in atomic percent, of from about 45 to about67 percent total of zirconium plus titanium, from about 10 to about 35percent beryllium, and from about 10 to about 38 percent total of copperplus nickel, plus incidental impurities, the total of the percentagesbeing 100 atomic percent. A substantial amount of hafnium may besubstituted for some of the zirconium and titanium, aluminum may besubstituted for the beryllium in an amount up to about half of theberyllium present, and up to a few percent of iron, chromium,molybdenum, or cobalt may be substituted for some of the copper andnickel. This bulk-solidifying alloy is known and is described in U.S.Pat. No. 5,288,344. A most preferred such metal alloy material, termedVitreloy™-1, has a composition, in atomic percent, of about 41.2 percentzirconium, 13.8 percent titanium, 10 percent nickel, 12.5 percentcopper, and 22.5 percent beryllium.

Another such metal alloy family material has a composition, in atompercent, of from about 25 to about 85 percent total of zirconium andhafnium, from about 5 to about 35 percent aluminum, and from about 5 toabout 70 percent total of nickel, copper, iron, cobalt, and manganese,plus incidental impurities, the total of the percentages being 100atomic percent. A most preferred metal alloy of this group has acomposition, in atomic percent, of about 60 percent zirconium about 15percent aluminum, and about 25 percent nickel. This alloy system is lesspreferred than that described in the preceding paragraph, because of itsaluminum content. Other bulk-solidifying alloy families, such as thosehaving even high contents of aluminum and magnesium, are operable buteven less preferred.

The use of bulk-solidifying amorphous alloys in golf club shafts and/orclub heads offers some surprising and unexpected advantages overconventional metals, metallic composites, and nonmetallic compositesused as materials of construction. The bulk-solidifying amorphous alloysexhibit a large fully-elastic deformation without any yielding, as shownin FIG. 4 for the case of Vitreloy™-1. This bulk-solidifying amorphousalloy strains 2 percent and to a stress of about 270 ksi (thousands ofpounds per square inch) without yielding, which is quite remarkable fora bulk material. The energy stored when the material is stressed to theyield point, sometimes termed U_(d), is 2.7 ksi. By comparison, acurrent titanium alloy popular in some advanced golf club shafts andheads yields at a strain of about 0.65 percent and a stress of about 110ksi, with a stored energy U_(d) to the yield point of about 0.35 ksi.The best prior material for energy storage, a copper-beryllium alloy,has a U_(d) of about 1.15 ksi, less than half that of the preferredbulk-solidifying amorphous alloy.

Another important material property affecting the performance of theclub head is the energy dissipation in the club head as the ball is hit.Many metallic alloys experience microyielding in grains oriented forplastic microslip, even at applied stresses and strains below the yieldpoint. For many applications the microyielding is not an importantconsideration. However, when the material is used in a club head facewhere there is a large impact force at the moment the club head hits thegolf ball, the microyielding absorbs and dissipates energy thatotherwise would be transferred to the ball.

FIG. 5 illustrates the deformation behavior of aircraft quality, forgedand heat-treated titanium-6 weight percent aluminum-4 weight percentvanadium (Ti-6AI-4V), a known material for use in golf-club heads, ascompared with that of the Vitreloy™-1 alloy, when strained to a levelapproximately indicative of local strains experienced by the club headface of a driver during impact with the golf ball. Yielding is evidencedby a hysteresis in the cyclic stress-strain curve upon repeated loadingand reverse loading, even when the loading is below the macroscopicyield point (a phenomenon termed “microyielding”). The Ti-6AI-4Vexhibits extensive hysteresis resulting from the yielding andmicroyielding. The Vitreloy™-1 bulk-solidifying amorphous alloy exhibitsno hysteresis upon repeated loading and reverse loading. The absence ofhysteresis in the loading behavior of the Vitreloy™-1 alloy results fromthe amorphous microstructure of the material wherein there are no grainsor other internal structures which exhibit microplastic deformation andconsequently microyielding during loading and reverse loading. Thisdifference in behavior of conventional polycrystalline club head alloysand the amorphous alloys is further verified by improved performance inbounce tests wherein a metal ball is dropped onto the surface of thematerial. The bounce is significantly higher for the amorphous alloysthan for the polycrystalline alloys, indicating less (and in fact,substantially no) energy absorption for the amorphous alloys andsignificant energy absorption for the polycrystalline alloys.

The desirable deformation behavior of the material of the club madeaccording to the invention may be characterized as an elastic strainlimit of at least about 1.5 percent, preferably greater than about 1.8percent, and most preferably about 2.0 percent, with an accompanyingplastic strain of less than about 0.01 percent, preferably less thanabout 0.001 percent up to the elastic strain limit. That is, thematerial exhibits substantially no plastic deformation when loaded toabout 80 percent of its fracture strength.

The bulk-solidifying amorphous alloys have excellent corrosionresistance due to the absence of grain boundaries. They have as-castsurfaces that are very smooth, when cast against a smooth surface, andhave low coefficients of friction. The smooth surface is attractive inappearance, and the low coefficients of friction reduce the bite on theball which would tend to cause it to follow a hook or slice trajectory.The amorphous alloys may be readily cast as club shafts or heads using anumber of techniques, most preferably permanent mold casting, permittingfabrication of the components at reasonable cost.

The preferred alloys used in the golf club have an exceedingly highstrength-to-density ratio, on the order of twice that of metalscurrently used in golf club heads such as steel and Ti-6AI-4V alloy.This property of the materials may be characterized as astrength-to-density ratio of at least about 1×10⁶ inches, and preferablygreater than about 1.2×10⁶ inches. This feature, together with the highelastic limit (FIG. 4) of the amorphous material and its low dampingproperties (FIG. 5), permits a surprising and unexpected redesign of thegolf club head to achieve improved performance.

For example, the club head face (30 and/or 30′) of the club head, whichis near the point of impact of the ball, may be reduced in thickness, sothat its mass may be redistributed to the periphery of the club headface and the club head. This redesign in turn gives the golf club head agreater moment of inertia about the point of impact, which leads to agreater stability against unwanted twisting motions of the club head.The redesign is accomplished without changing the overall mass of theclub head. A club head face made with conventional steel or titaniummaterials is typically about 3 millimeters or more thick, so that itdoes not plastically buckle upon ball impact. A club head face made ofthe amorphous material of the invention may be made less than 2.5millimeters thick, and most preferably in the range of from about 1.5 toabout 2 millimeters thick. If it is less thick, there is a risk ofplastic buckling upon impact. If it is thicker, the advantages discussedherein are lost. The thin club head face results in a “soft” feel to theclub when a ball is impacted. The mass saved as a result of thereduction in thickness of the club head face may be redistributed to theperiphery of the club head face or elsewhere at the periphery of theclub, thereby providing the increased moment of inertia and greaterstability discussed previously.

FIGS. 6A and 6B depict a particularly desirable application of theinvention to a set of golf clubs. Within a set of clubs having drivers,irons, and a putter, the volumes of the club heads may varyconsiderably. For example, a typical 3-iron illustrated in FIG. 6A has avolume of about 31.2 cubic centimeters (cc), and a typical 8-ironillustrated in FIG. 6B has a volume of about 35.6 cc. The shapes of theclub heads and thence their volumes are determined primarily byspecifications established by the professional golfing associations.There is a trend, however, to the use of larger irons. When the two clubheads are made of the same material, such as a conventional metal alloy,the weight of each club head varies proportionally to its volume.

The density properties of bulk-solidifying amorphous alloys offer twoimportant advantages to the design of golf-club heads, not availablewith other candidate materials. The first is the absolute value of thedensity range of the materials, and the second is the ability to varythe density over a wide range while maintaining other pertinentmechanical and physical properties within acceptable ranges. As to theabsolute value of the density range, the densities of the preferredbulk-solidifying amorphous alloys are from about 5.0 grams per cc toabout 7.0 grams per cc. These densities may be compared with thedensities of conventional candidate golf-club head materials such ascopper-beryllium, density 8.0 grams per cc; steel, density 7.8 grams percc; titanium, density 4.5 grams per cc; and aluminum, density 2.7 gramsper cc. The densities of these conventional materials are relativelyconstant and cannot be readily varied. There is a large gap in densitybetween copper-beryllium and steel, at the upper end, and titanium. Thepresent alloys lie in this gap region of density. Their use permits, forexample, an iron to have a larger size and volume than a steel iron, butto have about the same weight.

The second significant virtue of the use of amorphous alloys tomanufacture the club heads is that their densities may be selectivelyvaried over a moderately wide range of values. For example, within thebroad composition range of the preferred alloy (having a composition, inatom percent, of from about 45 to about 67 percent total of zirconiumplus titanium, from about 10 to about 35 percent beryllium, and fromabout 10 to about 38 percent total of copper plus nickel, plusincidental impurities, the total of the percentages being 100 atomicpercent), the densities may be varied from about 5.0 grams per cc toabout 7 grams per cc by changing the compositions while staying in thepermitted range that results in a bulk-solidifying amorphous alloy.

A range of particular interest to the inventors is from about 5.7 gramsper cc to about 6.2 grams per cc. Compositions of the bulk-solidifyingamorphous alloys within the preferred range that yield densities withinthe range of particular interest are shown in the following table:Composition (atomic %) Density Zr Cu Ti Ni Be 6.2 44.4 13.5 10.9 10.420.8 6.0 37.3 9.7 18.9 9.3 24.8 5.9 35.6 8.9 20.3 9.3 25.9 5.7 29.6 8.327.7 8.1 26.3

This ability to vary the density of the metal is used to advantage byselecting the composition of the bulk-solidifying amorphous alloy sothat its density times the volume of the club head, the total weight ofthe club head, meets a design value established by the club designer.The present inventors are not golf-club head designers, and thefollowing examples are prepared for illustration purposes only. If afirst club head (e.g., a 2-iron) has a design volume of about 39.3 ccand a second club head (e.g., an 8-iron) has a design volume of about42.7 cc, to maintain the two club heads of approximately constant weightof 244 grams, the first club head may be made of the bulk-solidifyingamorphous alloy having a density of 6.2 grams per cc and the second clubhead may be made of the bulk-solidifying amorphous alloy having adensity of about 5.7 grams per cc. The preceding table givescompositions suitable for achieving these densities. Because thecompositions of both alloys are selected within the permissible range ofthe bulk-forming amorphous alloys, the club heads will both be amorphousand will be of about the same total weight (the product of density ofthe material times the volume of the club head) and of comparablematerials properties such as discussed previously. These principles aredirectly extended to multiple clubs of the set having heads of differentvolumes.

In other cases, the club-head designer may not wish to achieve constantweights, but instead to have the weights vary in some selected fashion.To continue with the prior example, if the 2-iron having a volume of39.3 cc is made of the bulk-solidifying amorphous alloy having a densityof 5.7 grams, its weight would be 224 grams, a more suitable weight forpersons of smaller stature. If the 8-iron of volume 42.7 cc is made ofthe bulk-solidifying amorphous alloy having a density of 6.2 grams, itsweight would be 265 grams, a weight more suitable for persons of largerstature. In all cases, the club heads are made of the amorphous alloyswith their superior properties, and which may be cast using the same2-iron and 8-iron molds by permanent-mold casting. In the example, thisrange of properties is achieved using only variations of the densitiesfrom 5.7 to 6.2 grams per cc. The compositions of alloys within thepreferred bulk-solidifying amorphous alloy family permits significantlywider variations of about 5.0 to about 7.0 grams per cc, so that evenwider variations in weights are possible.

From these illustrative examples, it is apparent that the golf-clubdesigner has available an important new approach by which golf clubs maybe designed both as to their physical configuration and size (and thencevolume) and an independently selected material density. The selection ofthese characteristics permits the golf clubs to be tailored toindividual performance and characteristics of golfers.

Although a particular embodiment of the invention has been described indetail for purposes of illustration, various modifications andenhancements may be made without departing from the spirit and scope ofthe invention. Accordingly, the invention is not to be limited except asby the appended claims.

1. A golf club, comprising: a club shaft; and a club head, at least oneof the club shaft and the club head being made at least in part of abulk-solidifying amorphous metal that may be cooled from the melt at acooling rate of about 500° C. per second or less, yet retain anamorphous structure.
 2. The golf club of claim 1, wherein at least apart of the club shaft is made of a bulk-solidifying amorphous metal. 3.The golf club of claim 1, wherein at least a part of the club head ismade of a bulk-solidifying amorphous metal.
 4. The golf club of claim 3,wherein the golf club head is a driver club head.
 5. The golf club ofclaim 3, wherein the golf club head is an iron club head.
 6. The golfclub of claim 3, wherein the golf club head is a putter club head. 7.The golf club of claim 1, wherein the club head has a club head facemade of a bulk-solidifying amorphous metal.
 8. The golf club of claim 7,wherein the club head face has a thickness of less than about 2.5millimeters.
 9. The golf club of claim 7, wherein the club head face hasa thickness of from about 1.5 to about 2.0 millimeters.
 10. The golfclub of claim 1, wherein the bulk-solidifying amorphous metal has acomposition, in atomic percent, of from about 45 to about 67 percenttotal of zirconium plus titanium, from about 10 to about 35 percentberyllium, and from about 10 to about 38 percent total of copper plusnickel, plus incidental impurities, the total of the percentages being100 atomic percent.
 11. The golf club of claim 1, wherein thebulk-solidifying amorphous metal has a composition, in atomic percent,of from about 25 to about 85 percent total of zirconium and hafnium,from about 5 to about 35 percent aluminum, and from about 5 to about 70percent total of nickel, copper, iron, cobalt, and manganese, plusincidental impurities, the total of the percentages being 100 atomicpercent.
 12. The golf club of claim 1, wherein the bulk-solidifyingamorphous alloy exhibits substantially no plastic deformation whenloaded to about 80 percent of its fracture strength.
 13. The golf clubof claim 1, wherein the bulk-solidifying amorphous alloy has an elasticstrain limit of at least about 1.5 percent strain.
 14. The golf club ofclaim 1, wherein the bulk-solidifying amorphous alloy has astrength-to-density ratio of at least about 1×10⁶ inches.
 15. A golfclub, comprising: a club shaft; and a club head attached to the clubshaft, wherein at least part of the club head is made of abulk-solidifying amorphous metal that may be cooled from the melt at acooling rate of about 500° C. per second or less, yet retain anamorphous structure.
 16. The golf club of claim 15, wherein thebulk-solidifying amorphous metal has a composition, in atomic percent,of from about 45 to about 67 percent total of zirconium plus titanium,from about 10 to about 35 percent beryllium, and from about 10 to about38 percent total of copper plus nickel, plus incidental impurities, thetotal of the percentages being 100 atomic percent.
 17. The golf club ofclaim 15, wherein the bulk-solidifying amorphous metal has acomposition, in atomic percent, of from about 25 to about 85 percenttotal of zirconium and hafnium, from about 5 to about 35 percentaluminum, and from about 5 to about 70 percent total of nickel, copper,iron, cobalt, and manganese, plus incidental impurities, the total ofthe percentages being 100 atomic percent.
 18. A golf club, comprising: aclub shaft; and a driver club head attached to the club shaft, whereinat least part of the driver club head is made of a bulk-solidifyingamorphous metal that may be cooled from the melt at a cooling rate ofabout 500° C. per second or less, yet retain an amorphous structure. 19.The golf club of claim 18, wherein the bulk-solidifying amorphous metalhas a composition, in atomic percent, of from about 45 to about 67percent total of zirconium plus titanium, from about 10 to about 35percent beryllium, and from about 10 to about 38 percent total of copperplus nickel, plus incidental impurities, the total of the percentagesbeing 100 atomic percent.
 20. The golf club of claim 18, wherein thebulk-solidifying amorphous metal has a composition, in atomic percent,of from about 25 to about 85 percent total of zirconium and hafnium,from about 5 to about 35 percent aluminum, and from about 5 to about 70percent total of nickel, copper, iron, cobalt, and manganese, plusincidental impurities, the total of the percentages being 100 atomicpercent.